EP1349823B1 - Verfahren für basen-unterstützte kondensationsreaktionen sowie basenreagens dafür - Google Patents

Verfahren für basen-unterstützte kondensationsreaktionen sowie basenreagens dafür Download PDF

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Publication number
EP1349823B1
EP1349823B1 EP02700985A EP02700985A EP1349823B1 EP 1349823 B1 EP1349823 B1 EP 1349823B1 EP 02700985 A EP02700985 A EP 02700985A EP 02700985 A EP02700985 A EP 02700985A EP 1349823 B1 EP1349823 B1 EP 1349823B1
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Prior art keywords
alkali metal
alkyl
benzoyl
diketone
ethyl
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English (en)
French (fr)
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EP1349823A1 (de
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Michael H. Fisch
Edward Krainer
Radu Bacaloglu
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Lanxess Solutions US Inc
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Chemtura Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/68—Preparation of metal alcoholates
    • C07C29/70—Preparation of metal alcoholates by converting hydroxy groups to O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • This invention relates to a process for the preparation of beta-diketones and, more particularly, to a process for the production of beta-diketones by means of a homogeneous or nearly homogeneous liquid reaction medium wherein a carboxylic acid ester is reacted with a ketone in the presence of a condensing agent that is preferably a sterically hindered alkali metal alkoxide dissolved in an aromatic hydrocarbon.
  • Beta-diketones are highly valuable compounds having advantageous utility in a wide variety of applications.
  • U.S. Patent No. 3,001,970 discloses the use of dibenzoylmethane to prevent the discoloration of vinylidene chloride.
  • U.S. Patent No. 3,493,536 discloses that diaroylmethane compounds provide stabilizing action against the sensitizing effect of bismuth or antimony compounds on chlorine containing materials.
  • Aryl substituted beta-diketones are shown by U.S. Patent No. 3,994,869 to be useful as accelerators for the photodegradation of polyolefins.
  • U.S. Patent No. 4,427,816 discloses beta-diketones in combination with hydrotalcites as stabilizer compositions for halogen containing polymers.
  • acylation of ketones is a reaction that does not readily proceed in an economical manner.
  • acylation of ketones with esters in the presence of a basic reagent may be accompanied by certain side reactions.
  • side reactions that may occur are self-condensation of the ketone, self-condensation of the ester, aldol reaction of the ester with the carbonyl group of the ketone, or a Michael condensation of the ketone.
  • the basic condensing agent may react with the carbonyl group of the ester.
  • the reaction of the ester, the ketone, and the basic condensing agent in the presence of an inert solvent is known, as in the aforementioned Organic Reactions article at page 112.
  • This article further states that the beta-diketone may be isolated by the usual technique of distillation or filtration, but often it is isolated as its copper derivative from which the beta-diketones need to be regenerated by further chemical reactions with concomitant yield losses, generation of waste products, and laborious recovery of copper.
  • U.S. Patent No. 3,994,869 discloses the preparation of aryl substituted beta-diketones by the reaction of acetophenone or a substituted acetophenone with an ester in the presence of a base, such as sodium methoxide, sodium ethoxide, and sodium hydride.
  • the acetophenone may be represented by the structural formula: wherein R is selected from the group consisting of hydrogen, halogen, C 1 to C 9 alkyl and C 1 to C 9 alkoxy.
  • Representative esters identified as useful in this reaction are methyl stearate, ethyl benzoate, ethyl acetate, and ethyl laurate.
  • This reaction according to the patent, can be carried out in a suitable aprotic solvent, such as toluene or tetrahydrofuran. Recovery of the desired product is stated to be by methods that are now known in the art.
  • beta-diketones can be made by the reaction of acetophenone or a substituted acetophenone with an ester in the presence of base, this procedure has drawbacks which have limited its commercial acceptability.
  • U.S. Patent No. 4,482,745 discloses that handling large quantities of strong bases, such as sodium ethoxide makes their use undesirable and costly for large scale production.
  • sodium alkoxides are preferred bases since only one mole is consumed, whereas two moles of metallic sodium, sodium amide, or sodium hydride would normally be required. Then, too, metallic sodium or sodium hydride are more hazardous than the alkoxides.
  • Aromatic beta-diketones in high yields and purity can be readily made by this process.
  • the method taught by this patent comprises reacting acetophenone with from 5 to 10 molar equivalents of methyl benzoate in the presence of from 1 to 2 molar equivalents of calcium oxide, in a temperature range of from 150 ° to 200 ° C for from three to six hours under an inert nitrogen atmosphere while continuously removing the methyl alcohol which is formed during the reaction.
  • U.S. Patent No. 5,015,777 and European Patent No. 0 507 013 B1 disclose a process for the preparation of aromatic beta-diketones by the reaction of an acetophenone and a molar excess of an alphatic ester or an ester of benzoic acid in the presence of sodium alkoxide condensation agent in an aromatic hydrocarbon solvent. Also disclosed is a method of recycling the solvent and excess ester reactant after separation of the aromatic beta-diketone product.
  • U.S. Patent No. 5,344,992 and European Patent No. 0 454 624 B1 disclose a process for the preparation of 1,3-diketones of formula I wherein R 1 and R 2 are each independently of the other C 1 -C 20 alkyl, phenyl or phenyl which is substituted by halogen, hydroxy, NO 2 C 1 -C 4 alkyl and/or C 1 -C 4 alkoxy, C 7 -C 9 phenylalkyl or a radical of formula II -A-X-R 4 (II) wherein A is C 1 -C 12 alkylene, phenylene or phenylene which is substituted by halogen, hydroxy, NO 2 C 1 -C 4 alkyl and/or C 1 -C 4 alkoxy, or is C 1 -C 12 alkylene which is substituted by hydroxy, halogen and/or alkoxy, X is oxygen or sulfur, and R 4 is hydrogen, C 1 -C 18 alkyl,
  • the process comprises carrying out a Claisen condensation of a ketone of formula III and an ester of formula IV or wherein m is 2 to 10 and R 5 is C 1 -C 5 alkyl, phenyl or phenyl which is substituted by halogen, C 1 -C 4 alkyl or hydroxy, the reaction being carried out with the base used as catalyst, a hydride of an alkali metal or alkaline earth metal or an alcoholate of C 1 -C 5 alkali metal or C 1 -C 5 alkaline earth metal, in a mixture of dimethyl sulfoxide and at least one organic solvent which is inert under the reaction conditions.
  • the use of dimethyl sulfoxide is a disadvantage owing to the difficulty of completely removing it from the product and of recovering it for reuse without significant losses.
  • U.S. Patent No. 5,672,646 discloses a stabilizing composition for a chlorine-containing polymer (PVC), characterized in that it comprises the unpurified crude product resulting from the reaction of an ester with a ketone in the presence of an alkaline agent, this crude product comprising at least 10 % by weight of ⁇ -diketone and being in the form of a powder.
  • PVC chlorine-containing polymer
  • U.S. Patent No. 5,808,165 discloses compositions containing beta-diketones of formula (I) and formula (II), R 1 COCH 2 COR 2 (I) R 2 COCH 2 COR 2 (II) which may be used to stabilize various polymers, such as polyvinyl chlorides (PVCs), in which R 1 is represented by the formula (Y) n - ⁇ -, wherein ⁇ is phenyl and each Y, which may be the same or different, is a hydrogen atom or a group selected from hydrocarbon chains having 1 to 12 carbon atoms, alkoxys, silyls and nonreactive halogen atoms; each R 2 , which may be the same or different, represents a hydrogen atom or a group selected from hydrocarbon chains having 1 or 5 to 12 carbon atoms, which may be interrupted by one or more oxygen atoms, aralkyls, alkoxys and silyls; and n represents an integer from 0 to 3; with the proviso that if
  • EP 0 697 390 A1 discloses a method for the preparation of 1,3-diketones, however, without thorough purification or final purification.
  • DBM Dibenzoylmethane
  • alkylaryl 1,3-diketones can be obtained by using sodium methoxide only with low yields.
  • the condensation of methyl stearate with acetophenone using sodium methoxide yields only about 50% of benzoylstearoylmethane (SBM).
  • a process of preparing a 1,3-diketone from a carboxylic acid ester and a ketone by a condensation reaction promoted by a basic condensing agent that overcomes the problems outlined above by using a basic condensing agent that is soluble in an aromatic hydrocarbon and is an alkali metal alkoxide of an alcohol having a boiling point of at least 100° C at atmospheric pressure as defined in claim 1.
  • a basic condensing agent consisting essentially of a solution of alkali metal alkoxide of an alcohol having a boiling point of at least 100°C at atmospheric pressure in an aromatic hydrocarbon.
  • the expression "consisting essentially of is used to indicate that polar aprotic solvents such as dimethyl sulfoxide are unnecessary and objectionable according to this invention.
  • the alcohol used in preparing the basic condensing agent is regenerated in the preparation of the 1,3-diketone, and can be readily recovered and reused to prepare additional alkali metal alkoxide by reaction with alkali metal hydroxide according to the invention. Consequently, from an economic standpoint the only base consumed is alkali metal hydroxide, which offers significant savings over prior art sodium methoxide and other basic condensing agents.
  • the present invention is directed to a method for the preparation of 1,3-diketones comprising the steps of:
  • the process of the present invention is a Claisen condensation comprising the following steps:
  • the sodium or potassium salt of the diketone can, in some cases, be isolated by filtration before acidifying the reaction mixture.
  • the solid diketone salt can then be neutralized by slowly adding it with stirring to a mixture of water and an aromatic hydrocarbon.
  • an acid such as acetic acid, is added to keep the pH neutral at all times.
  • the organic layer can then be washed and the solvent stripped.
  • the 1,3-diketones prepared in accordance with this invention are preferably linear 1,3-diketones of general formula I wherein R 1 and R 2 are independently selected from the group consisting of C 1 -C 20 alkyl; phenyl; phenyl that is substituted by halogen, hydroxy, NO 2 , C 1 -C 4 alkyl and/or C 1 -C 4 alkoxy; C 7 -C 9 phenylalkyl; and radicals of formula II -A-X-R 4 (11) wherein A is selected from the group consisting of C 1 -C 12 alkylene; C 1 -C 12 alkylene that is substituted by hydroxy, halogen and/or alkoxy; phenylene; and phenylene that is substituted with halogen, hydroxy, NO 2 , C 1 -C 4 alkyl and/or C 1 -C 4 alkoxy; X is oxygen or sulfur; R 4 is selected from the group consisting of hydrogen; C 1 -C 18
  • R 1 and/or R 2 are C 1 -C 20 alkyl, they may be linear or branched and are typically methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and isomers and mixtures thereof.
  • They are preferably C 1 -C 18 alkyl, such as methyl, isopentyl, n-nonyl, pentadecyl or heptadecyl.
  • R 1 and/or R 2 are substituted phenyl, they preferably contain from 1 to 3, more preferably 1 or 2 substituents, most preferably one substituent.
  • R 1 and/or R 2 are (C 1 -C 4 alkyl)phenyl, they are preferably phenyl substituted by 1 to 3, more preferably 1 or 2, alkyl groups, which are most preferably methyl groups. Typical examples include tolyl, xylyl, or mesityl.
  • R 1 and/or R 2 are halogen-substituted phenyl, they may be a phenyl ring that is substituted by one or more identical or different members selected from the group consisting of fluoro, chloro, and bromo, preferably chloro or bromo, and are typically chlorophenyl or dichlorophenyl:
  • R 1 and/or R 2 are C 1 -C 4 alkoxy-substituted phenyl, they are typically methoxyphenyl, ethoxyphenyl, propoxyphenyl, butoxyphenyl, and isomers thereof.
  • R 1 and/or R 2 are C 7 -C 9 phenylalkyl, they may be, for example, benzyl, phenylethyl, ⁇ -methylbenzyl, 3-phenylpropyl, or ⁇ , ⁇ -dimethylbenzyl. Benzyl is preferred.
  • R 1 and/or R 2 are preferably C 1 -C 18 alkyl, phenyl, (C 1 -C 4 alkyl)phenyl, or -A-X-R 4 .
  • A is C 1 -C 12 alkylene, it can be either linear or branched, but is preferably linear, alkylene.
  • Typical examples of such radicals include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptalene, octalene, nonalene, decylene, undecylene, dodecylene, and isomers thereof.
  • Alkylenes of from 1 to 6 carbon atoms are preferred, and n-propylene or n-pentylene are most preferred.
  • A is unsubstituted or substituted phenylene, it is preferably o- or p-phenylene, more preferably, A is unsubstituted phenylene.
  • R 4 is C,-C,g alkyl, it may be linear or branched alkyl, as exemplified above in connection with R 1 and R 2 up to the corresponding number of carbon atoms.
  • R 4 is substituted phenyl or C 7 -C 9 phenylalkyl, it can have the same meanings as given for R 1 and R 2 .
  • R 4 is preferably hydrogen, C 1 -C 18 alkyl, or phenyl.
  • R 3 is C 1 -C 20 alkyl, substituted phenyl, or C 7 -C 9 phenylalkyl, it can have the same meanings as given for R 1 and R 2 .
  • R 3 is preferably hydrogen or C 1 -C 4 alkyl, e.g., methyl, ethyl, propyl, butyl, or isomers thereof, but is more preferably hydrogen.
  • R 5 is C 1 -C 5 alkyl, it can be methyl, ethyl, propyl, butyl, butyl, pentyl, or isomers thereof. More preferably, R 5 is C 1 -C 4 alkyl, most preferably, methyl.
  • R 5 is (C 1 -C 4 alkyl)phenyl, it can have the same meanings as those given for R 1 and R 2 .
  • the basic condensing agent according to the invention is an alkali metal alkoxide of an alcohol, said alcohol having a boiling point of at least 100° C at atmospheric pressure.
  • the alkali metal of the alkoxide is any one or more of the alkali metals. Sodium and potassium alkoxides are preferred.
  • the alcohol with a boiling point of at least 100°C at atmospheric pressure can be primary, secondary, or tertiary, and can have 1-2 alcoholic hydroxyl groups.
  • the alcohol can be aliphatic or cycloaliphatic, and can also be substituted with alkoxy groups having 1 to 5 carbon atoms and with aryl groups. Alkoxides of alcohols having a sterically hindered structure are particularly preferred.
  • Preferred alkoxides are the sodium and potassium alkoxides of 1-butanol, 1-pentanol, cyclohexanol, 2-methyl-2,4-pentanediol, 2- propoxy-1-ethanol, 1-methoxy-2-propanol, I-t-butoxy-2-propanol, 2-ethyl-1- hexanol, 1-phenylethanol, benzhydrol, triphenylmethanol, tert.-pentanol, 1-octanol, and 2-octanol, and the like.
  • the alkali metal alkoxide condensing agent can be prepared by reaction of the selected alcohol in the presence of aromatic hydrocarbon with such source of metal base as alkali metal or alkali metal hydride, with displacement of hydrogen; alkali metal amide, with displacement of ammonia; and lower alkali metal alkoxide, with displacement of lower alcohol.
  • the alkali metal alkoxide condensing agent can also be prepared by dissolving a separately prepared alkali metal alkoxide of the selected alcohol in an aromatic hydrocarbon.
  • the alkali metal alkoxide is prepared according to the invention by reaction of the selected alcohol with alkali metal hydroxide, preferably sodium or potassium hydroxide, as the alkali metal base, with displacement of water.
  • alkali metal hydroxide preferably sodium or potassium hydroxide
  • This can be advantageously carried out by heating a mixture of the selected alcohol, alkali metal hydroxide, and aromatic hydrocarbon solvent such that the water formed is distilled azeotropically, while maintaining a slow stream of nitrogen over the reaction mixture.
  • ketones of formula III are employed as starting materials in the process of the present invention.
  • Ketones that can be employed include aliphatic-aromatic, aliphatic-aliphatic, and cycloaliphatic ketones, such as acetophenone, acetone, methyl ethyl ketone, methyl n-propyl ketone, diethyl ketone, hexanone-2, pinacolone, di-n-propyl ketone, diisopropyl ketone, di-n-amyl ketone, chloroacetone, s -dichloroacetone, cyclohexanone, cyclopentanone, and the like.
  • esters of formula IV wherein R 5 is selected from the group consisting of C 1 -C 5 alkyl; phenyl; and phenyl that is substituted with halogen, C 1 -C 4 alkyl, or hydroxy; or, if R 2 in formula I is -(CH 2 ) m OH, also with cyclic esters of formula V wherein m is an integer of from 2 to 10.
  • esters include, for example, aromatic esters, such as methyl benzoate, and aliphatic esters, such as ethyl acetate, methyl esters of linear C 8 to C 18 carboxylic acids, such as methyl stearate, methyl palmitate, methyl caprylate, mixtures of aliphatic esters, and the like.
  • Alcohols e.g., methanol
  • aromatic beta-diketones can be prepared.
  • aromatic beta-diketones are dibenzoylmethane, benzoyl 2,4-methylenedioxy benzoylmethane; benzoyl 3,5-dimethylbenzoyl methane; benzoyl 3-methylbenzoy I methane; benzoyl 4-methyl benzoylmethane; 3-methylbenzoyl 4-methylbenzoylmethane; benzoyl 4-chlorobenzoylmethane; benzoyl 2-bromobenzoylmethane; benzoyl 3,5-dichlorobenzoylmethane; benzoyl 2-nitrobenzoylmethane; benzoyl-2,3,4-trimethylbenzoylmethane; benzoyl-2,3,5-trichlorobenzoylmethane; benzoylstearoylmethane; 3-methylbenzoylstearoylmethane 3,4-dichlorobenzoylstearoylmethane benzoyl hept
  • acetophenone-type reactant is preferably selected.
  • useful acetophenone reactants are acetophenone; o-, m-, or p-methylacetophenone; o-, m-, or p-methoxy acetophenone; o-, m-, or p-methylthioacetophenone, o-, m-, or p-nitroacetophenone; 3,4-(methylenedioxy) acetophenone, o-, m-, or p-chloroacetophenone; o-, m-, or p-bromoacetophenone; 2,4-diethylacetophenone; 2,3,5-trichloroacetophenone, 2,3-dibromoacetophenone; 2,4-dimethoxyacetophenone; 2,4-propoxyacetophenone; 2,3-dimethylthioacetophenone;
  • the ester reactant is selected on the basis of the identity of the desired beta-ketone.
  • an ester of benzoic acid can be used. Since the condensation reaction has as its by-product an alcohol formed from the ester group, normally there is no benefit from using higher alkyl esters. Accordingly, lower alkyl esters of benzoic acid are satisfactory, although higher esters can be used, if desired.
  • the term "lower" means alkyl groups having up to about 5 carbon atoms.
  • benzoate reactants are methylbenzoate; ethyl benzoate; propylbenzoate; butylbenzoate; pentylbenzoate; methyl o-,m- or p-methylbenzoate; ethyl o-, m-, or p-chlorobenzoate; methyl o-, m-, or p-methylthiobenzoate; ethyl o-, m-, or p-methoxybenzoate; methyl o-, m-, or p- bromobenzoate; ethyl o-, m-, or p- nitrobenzoic acid; ethyl 2,3-dimethyl benzoate; propyl 2,5-diethylbenzoate; ethyl 2,3,4-tri-methylbenzoate; butyl-2,5-diethylthiobenzoate; ethyl 3,4-dimethoxybenzoate
  • the condensation reaction can be performed at various elevated temperatures.
  • temperatures between about 40° C and about 170° C, preferably about 90° C to about 120° C are normally used.
  • a temperature in the range of 90 to 120°C is used. At these temperatures maximum amounts of high quality beta-diketone products can be recovered by standard procedures.
  • ester reactant In order to obtain high quality product in high yield, it is desirable to use a molar excess of the ester reactant. This causes the reaction to proceed to about its theoretical maximum.
  • the preferred excess of ester reactant useful in this process varies somewhat with the identity of the ester reactant. Since the use of more than the necessary amount of ester reactant will often increase the loss of this reactant, it is preferred to maintain the ratio of ester reactant to acetophenone below about 8:1, more preferably below about 2:1. Ratios of the ester of benzoic acid to acetophenone of about 2:1 will normally produce optimum yields and purity of dibenzoylmethane.
  • the excess ester reactant can be recycled with the solvent so as to limit the reactant needs and reduce the cost of operating the process.
  • Aromatic hydrocarbons are preferably used as solvents for performing the process of the present invention. Since the temperature of the reaction is between about 100° C and about 170° C, it is desirable to use an aromatic hydrocarbon solvent having a boiling point within this temperature range so that the reaction can proceed at atmospheric pressure; however, aromatic hydrocarbons having lower or higher boiling points can be used by adjusting the pressure accordingly.
  • aromatic hydrocarbons useful as solvents in the practice of the process of the present invention are ethyl benzene, cymene, diethylbenzene, dimethylethylbenzene, amyltoluene, toluene, trimethylbenzene, cumene, tetralin, xylenes, and the like.
  • the 1,3-diketone is present in the reaction mixture in the form of an alkali metal salt.
  • the salt can be isolated from the reaction mixture by filtration and used as is or converted to other 1,3-diketone metal salts, for example aluminum, calcium, magnesium, and zinc salts, by reaction with a compound of the selected metal such as aluminum sulfate, calcium and magnesium chlorides, and zinc acetate.
  • the solid kidetone salt can also be neutralized to afford the free 1,3-diketone by slowly adding it with stirring to a mixture of water and an aromatic hydrocarbon while adding an acid, such as acetic acid, to keep the pH neutral.
  • the organic layer can then be washed and the solvent stripped.
  • the entire reaction mixture can be acidified with an excess of acid, which is then neutralized, and the solvent is stripped.
  • the alcohol reactant can be recovered together with the solvent or separately, by such techniques as distillation, crystallization or extraction with solvents as appropriate.
  • the diketone product if it is a solid, can be purified by crystallization.
  • the residue was transferred to a separatory funnel and washed with water.
  • the solvents were stripped in a Rotavap at 2 mm Hg, heating up to 145 ° C.
  • the distillate contains methyl benzoate for recovery.
  • Cumene (dry, 350 mL), sodium tert-pentoxide (35.8 g; 0.325 mol), and methyl benzoate (68.1 g; 0.50 mol) were placed into a four-necked, round bottom, one liter flask equipped with a stirrer, a thermometer, and a reflux condenser with a distillation valve. The mixture was heated to 120° C and kept at that temperature under a blanket of nitrogen.
  • Acetophenone (30.0 g; 0.25 mol) was added slowly over a period of 36 minutes by means of a syringe pump. Some solvent (37 mL total) was distilled out of the system as the reaction proceeded. A vacuum was applied to the system by means of a water aspirator to help with the distillation. After 1.4 hours from the beginning of the addition of the ketone, the mixture was cooled down to room temperature and filtered under vacuum. The sodium salt of DBM was washed with dry cumene.
  • Benzhydrol (104.3 g; 0.567 mol), potassium hydroxide (85.4%; 36.14 g; 0.550 mol) and cumene (375 mL) were placed into a four-necked, round bottom, one liter flask equipped with a stirrer, a thermometer, and an Oldershaw column with a Dean-Stark trap and a condenser.
  • Example 4 A procedure analogous to the one described in Example 4 was used for obtaining a mixture of 1,3-diketones, with benzoylstearoylmethane as the main component.
  • the methyl ester used as raw material was Kemester 7018 (Crompton), with a chain length distribution of C 14 : 4.4 weight percent; C 16 : 27.9%; C 17 : 2.6%; and C 18 : 61.4%.
  • the amount used was 122.4 g; 0.425 mol. Crystallization from methanol afforded 83.4 g of SBM (61 % yield) of purity higher than 99% (GC).
  • acetophenone 44.06 g; 0.367 mol
  • the mixture was allowed to cool to room temperature, and was acidified with 10% sulfuric acid.
  • the cumene layer was washed with water until the washes were neutral, and then concentrated under vacuum in a rotary evaporator.
  • the residue was treated with heptane, allowed to stand for a few minutes, and then filtered, affording pure benzhydrol (63.2 g; 61.1% yield). The heptane was removed under vacuum.
  • More benzhydrol was obtained by adding 500 mL of heptane, 500 mL of methanol, and 250 mL of water, stirring, removing the lower layer, and repeating this extraction several times. Upon evaporation of the lower layer under vacuum in a rotary evaporator, and washing the resulting crystals with heptane, 17.3 g of benzhydrol (16.7% yield) was obtained. Evaporation of the solvents in the upper layer afforded 80.0 g (85% yield) of CBM with a purity of over 95% (GC).
  • GC purity of over 95%
  • Cumene (dry, 180 mL), sodium tert-pentoxide (35.8 g; 0.326 mol), and methyl benzoate (68.1 g; 0.50 mol) were placed into a four-necked, round bottom, half-liter flask equipped with a stirrer, a thermometer, and a reflux condenser. The mixture was heated to 100° C and kept at that temperature under a blanket of nitrogen. Cyclohexanone (24.5 g; 0.250 mol) was added slowly over a period of 15 minutes by means of a syringe pump. After 20 minutes from the beginning of the addition of the ketone, the mixture was cooled with an ice water bath to room temperature.
  • 1-Methoxy-2-propanol (61.3 g; 0.68 mol), sodium hydroxide (16.0 g; 0.40 mol), and xylenes (300 mL) were placed into a four-necked, round bottom, half-liter flask equipped with a stirrer, a thermometer, and an Oldershaw column with a Dean-Stark trap and a condenser. The mixture was heated to boiling with stirring under a blanket of nitrogen and the water was azeotroped out (temperature of reflux 106-116° C).

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Claims (16)

  1. Verfahren zur Herstellung von 1,3-Diketonen, umfassend die Stufen von:
    (A) Bereitstellung eines Gemischs von einer Alkalimetallbase, einem aromatischen Kohlenwasserstoff und einem Alkohol, der einen Siedepunkt von mindestens 100°C bei Atmosphärendruck aufweist und ausgewählt ist aus der Gruppe, bestehend aus 1-Butanol, 1-Pentanol, Cyclohexanol, 2-Methyl-2,4-pentandiol, 2-Propoxy-1-ethanol, 1-Methoxy-2-propanol, 1-tert-Butoxy-2-propanol, 2-Ethyl-1-hexanol, 1-Phenylethanol, Benzhydrol, Triphenylmethanol, tert.-Pentanol, 1-Octanol und 2 Octanol;
    (B) Erwärmen des Gemischs und Entfernung von Nichtalkoxidnebenprodukt(en), gebildet durch Umsetzung der Alkalimetallbase und des Alkohols, wobei eine Lösung des Alkalimetallalkoxids in dem aromatischen Kohlenwasserstoff gebildet wird;
    (C) Mischen eines Carbonsäureesters mit der Lösung des Alkalimetallalkoxids;
    (D) Zugabe eines Ketons und Erwärmen bei einer Temperatur in dem Bereich von 90 bis 120°C bis die Bildung von 1,3-Diketon im Wesentlichen vollständig ist; und
    (E) Gewinnung des 1,3-Diketons aus dem Reaktionsgemisch.
  2. Verfahren nach Anspruch 1, wobei das 1,3-Diketon in der Form eines Alkalimetallsalzes davon gewonnen wird.
  3. Verfahren nach Anspruch 1, wobei das 1,3-Diketon als freies Diketon gewonnen wird.
  4. Verfahren nach Anspruch 3, wobei das Reaktionsgemisch angesäuert wird, überschüssige Säure neutralisiert wird, eine wässrige Phase von einer organischen Phase getrennt wird, und das 1,3-Diketon aus der organischen Phase gewonnen wird.
  5. Verfahren nach Anspruch 1, wobei die Alkalimetallbase ausgewählt wird aus der Gruppe, bestehend aus Alkalimetallhydroxiden, niederen Alkalimetallalkoxiden, Alkalimetallamiden, Alkalimetallhydriden und den Alkalimetallen.
  6. Verfahren nach Anspruch 1, wobei die Alkalimetallbase für ein Alkalimetallhydroxid steht.
  7. Verfahren nach Anspruch 6, wobei das Alkalimetallhydroxid für Natriumhydroxid oder Kaliumhydroxid steht.
  8. Verfahren nach Anspruch 1, wobei das aromatische Kohlenwasserstofflösemittel ausgewählt wird aus der Gruppe, bestehend aus Ethylbenzol, Cymol, Diethylbenzol, Dimethylethylbenzol, Amyltoluol, Toluol, Trimethylbenzol, Cumol, Tetralin und Xylolen.
  9. Verfahren nach Anspruch 1, wobei das Diketon die folgende Struktur aufweist
    Figure imgb0017
     wobei
    R1 und R2 unabhängig ausgewählt werden aus der Gruppe, bestehend aus C1-C20-Alkyl; Phenyl; Phenyl, das substituiert ist durch Halogen, Hydroxy, NO2, C1-C4-Alkyl und/oder C1-C4-Alkoxy; C7-C9-Phenylalkyl; und Resten der Formel II
    -A-X-R4 (II),
    wobei
    A ausgewählt wird aus der Gruppe, bestehend aus C1-C12-Alkylen; C1-C12-Alkylen, das substituiert ist durch Hydroxy, Halogen und/oder Alkoxy; Phenylen; und Phenylen, das substituiert ist durch Halogen, Hydroxy, NO2, C1-C4-Alkyl und/oder C1-C4-Alkoxy;
    X für Sauerstoff oder Schwefel steht;
    R4 ausgewählt wird aus der Gruppe, bestehend aus Wasserstoff; C1-C18-Aklyl; Phenyl; Phenyl, das substituiert ist durch Halogen, Hydroxy, C1-C4-Alkyl, NO2 und/oder C1-C4-Alkoxy; und C7-C9-Phenylalkyl; und R3 ausgewählt wird aus der Gruppe, bestehend aus Wasserstoff; C1-C20-Alkyl; Phenyl; Phenyl, das substituiert ist durch Halogen, Hydroxy, C1-C4-Alkyl, NO2 und/oder C1-C4-Alkoxy; und C7-C9-Phenylalkyl.
  10. Verfahren nach Anspruch 9, wobei das Keton die folgende Struktur aufweist
    Figure imgb0018
  11. Verfahren nach Anspruch 10, wobei das Keton ausgewählt wird aus der Gruppe, bestehend aus Acetophenon; o-, m- oder p-Methylacetophenon; o-, m- oder p-Methoxyacetophenon; o-, m- oder p-Methylthioacetophenon; o-, m- oder p-Nitroacetophenon; 3,4-(Methylendioxy)acetophenon; o-, m- oder p-Chloracetophenon; o-, m- oder p-Bromacetophenon; 2,4-Diethylacetophenon; 2,3,5-Trichloracetophenon; 2,3-Dibromacetophenon; 2,4-Dimethoxyacetophenon; 2,4-Propoxyacetophenon und 2,3-Dimethylthioacetophenon.
  12. Verfahren nach Anspruch 9, wobei der Ester die folgende Struktur aufweist
    Figure imgb0019
     wobei R5 ausgewählt wird aus der Gruppe, bestehend aus C1-C5-Alkyl; Phenyl und Phenyl, das substituiert ist durch Halogen, C1-C4-Alkyl oder Hydroxy;
    oder, wenn R2 für -(CH2)mOH steht, auch aus folgender Struktur
    Figure imgb0020
     wobei m für eine ganze Zahl von 2 bis 10 steht.
  13. Verfahren nach Anspruch 12, wobei der Ester für ein Benzoat steht.
  14. Verfahren nach Anspruch 13, wobei das Benzoat ausgewählt wird aus der Gruppe, bestehend aus Methylbenzoat; Ethylbenzoat; Propylbenzoat; Butylbenzoat; Pentylbenzoat; Methyl-o-, -m- oder -p-methylbenzoat; Ethyl-o-, -m- oder -p-chlorbenzoat; Methyl-o-, -m- oder -p-methylthiobenzoat; Ethyl-o-, -m- oder -p-methoxybenzoat; Methyl-o-, -m- oder -p-brombenzoat; Ethyl-o-, -m- oder -p-nitrobenzoesäure; Ethyl-2,3-dimethylbenzoat; Propyl-2,5-diethylbenzoat; Ethyl-2,3,4-tri-methylbenzoat; Butyl-2,5-diethylthiobenzoat; Ethy-3,4-dimethoxybenzoat; Methyl-2,3-dichlorbenzoat; Ethyl-2,4-dibrombenzoat; Propyl-2,3,5-trichlorbenzoat und Propyl-2,4-diethyloxybenzoat.
  15. Verfahren nach Anspruch 1, wobei das Diketon für ein aromatisches beta-Diketon steht.
  16. Verfahren nach Anspruch 15, wobei das aromatische beta-Diketon ausgewählt wird aus der Gruppe, bestehend aus Dibenzoylmethan; Benzoyl-2,4-methylendioxybenzoylmethan; Benzoyl-3,5-dimethylbenzoylmethan; Benzoyl-3-methylbenzoylmethan; Benzoyl-4-methylbenzoylmethan; 3-Methylbenzoyl-4-methylbenzoylmethan; Benzoyl-4-chlorbenzoylmethan; Benzoyl-2-brombenzoylmethan; Benzoyl-3,5-dichlorbenzoylmethan; Benzoyl-2-nitrobenzoylmethan; Benzoyl-2,3,4-trimethylbenzoylmethan; Benzoyl-2,3,5-trichlorbenzoylmethan; Benzoylstearoylmethan; 3-Methylbenzoylstearoylmethan; 3,4-Dichlorbenzoylstearoylmethan; Benzoylheptadecanoylmethan; 3-Methylbenzoyltetradecanoylmethan; 4-Chlornonadecoylmethan; 2-Methylbenzoyllauroylmethan; 3-Nitrobenzoylmyristoylmethan; 2,3-Ethoxybenzoylpalmitoylmethan; 2-Methoxybenzoylstearoylmethan und 3-Methylthiobenzoyl-2,3-butylmethan.
EP02700985A 2001-01-12 2002-01-08 Verfahren für basen-unterstützte kondensationsreaktionen sowie basenreagens dafür Withdrawn - After Issue EP1349823B1 (de)

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PCT/US2002/000011 WO2002055466A1 (en) 2001-01-12 2002-01-08 Process for base-promoted condensation reactions and base reagent therefor
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WO2022180269A1 (en) 2021-02-26 2022-09-01 Sun Chemical Corporation Photoinitiator resins with dibenzoylmethane substructure
WO2023118482A1 (en) 2021-12-24 2023-06-29 Sun Chemical Corporation Amine synergists with uv-a absorption

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CN102898303A (zh) * 2012-09-11 2013-01-30 安徽佳先功能助剂股份有限公司 一种从硬脂酰苯甲酰甲烷残液中提取硬脂酸甲酯的方法

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US1712830A (en) * 1923-10-20 1929-05-14 Nat Aniline & Chem Co Inc Alkali-metal alcoholates
GB1143897A (en) * 1967-02-17 1969-02-26 Metallgesellschaft Ag A process for preparing alkali metal alcoholates and phenolates
US5015777B1 (en) * 1989-11-02 1994-12-20 Witco Corp Process for the preparation of aromatic beta-diketones
EP0454624B1 (de) * 1990-04-26 1995-10-11 Ciba-Geigy Ag Verfahren zur Herstellung von 1,3-Diketonen
US5583269A (en) * 1993-09-30 1996-12-10 Fmc Corporation Method of preparation of lithium tertiary-butoxide
DE4427512A1 (de) * 1994-08-03 1996-02-08 Basf Ag Verfahren zur Herstellung von 1,3-Diketonen und deren Verwendung als Stabilisatoren für Kunststoffe

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WO2022180269A1 (en) 2021-02-26 2022-09-01 Sun Chemical Corporation Photoinitiator resins with dibenzoylmethane substructure
WO2023118482A1 (en) 2021-12-24 2023-06-29 Sun Chemical Corporation Amine synergists with uv-a absorption

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